Bonetti Marco, Dubois Alizée
Service de Physique de l'Etat Condensé CEA-SPEC, CNRS, Université Paris-Saclay, CEA Saclay, F-91191, Gif sur Yvette, France.
Laboratoire de Physique, ENS de Lyon, F-69342, Lyon, France.
Eur Phys J E Soft Matter. 2019 Aug 6;42(8):97. doi: 10.1140/epje/i2019-11861-4.
We address the problem of glass-forming of liquids by superpressing. We study the pressure-induced dynamic change of the fragile van der Waals liquid propylene carbonate towards the glassy state in the equilibrium regime by measuring the diffusivity of the fluorescent probe Coumarin 1 embedded in the host liquid. The probe diffusivity is measured by the fluorescence recovery after photobleaching (FRAP) technique across a bleached volume generated by the near-field diffracted pattern of a laser beam. The recovered fluorescence intensity fits to a stretched exponential with the diffusive time [Formula: see text] and the stretched exponent [Formula: see text] as free parameters. In the pressure range [0.3-1.0]GPa the diffusivity decouples from the Stokes-Einstein relation. The decoupling correlates well to a decrease of [Formula: see text]. The variation of [Formula: see text] is non-monotonous with [Formula: see text] showing a minimum at [Formula: see text] s. We evidence an isochronal superpositioning over about 3 decades of [Formula: see text] between ∼ 10 s and [Formula: see text] s and a density scaling in the whole investigated pressure range. The pressure at which [Formula: see text] is minimum coincides to the dynamical crossover pressure measured by other authors. This crossover pressure is compatible with the critical point of MCT theory. As our studied pressure range encompasses the critical pressure, the non-monotonous variation of [Formula: see text] opens new insight in the approach to the critical point.
我们通过超压处理来解决液体玻璃化形成的问题。我们通过测量嵌入主体液体中的荧光探针香豆素1的扩散率,研究了在平衡状态下,脆弱的范德华液体碳酸丙烯酯向玻璃态转变时压力诱导的动态变化。通过光漂白后荧光恢复(FRAP)技术,在由激光束近场衍射图案产生的漂白体积上测量探针扩散率。恢复的荧光强度拟合为拉伸指数,其中扩散时间[公式:见原文]和拉伸指数[公式:见原文]为自由参数。在[0.3 - 1.0]吉帕的压力范围内,扩散率与斯托克斯 - 爱因斯坦关系解耦。这种解耦与[公式:见原文]的降低密切相关。[公式:见原文]的变化与[公式:见原文]并非单调关系,在[公式:见原文]秒时出现最小值。我们证明了在约10秒至[公式:见原文]秒之间约3个数量级的[公式:见原文]的等时叠加以及在整个研究压力范围内的密度标度。[公式:见原文]取最小值时的压力与其他作者测量的动态交叉压力一致。这个交叉压力与MCT理论的临界点兼容。由于我们研究的压力范围涵盖了临界压力,[公式:见原文]的非单调变化为接近临界点的研究开辟了新的视角。